The discovery and development of new methods for the synthesis of tomorrow's cancer drugs is a crucial component of medicinal research. With the development of new methods, drug candidates can be prepared in a more rapid and efficient manner, necessary for drug discovery. This proposal investigates a new class of air-stable building blocks for use in synthesis. A key building block will function as a "linchpin", selectively joining two other segments of the target molecule. This approach will be demonstrated in the total synthesis of the novel antitumor agent, deoxyverrucosidin. Deoxyverrucosidin strongly inhibits glucose-regulated protein 78 (GRP78), a protein known (in vitro) to play a role in the protection and transport of solid tumors. This may allow milder anti-cancer drugs to be implemented since the defense mechanism and mode of transport are inhibited by this naturally occurring compound. The generality of this synthesis should provide both the target for further biological studies, as well as development of new analogs for fine-tuning its antitumor properties. [unreadable] [unreadable] [unreadable]